U.S. patent application number 15/557602 was filed with the patent office on 2018-02-15 for long fiber-reinforced polyarylene sulfide resin molded article and method for producing the same.
The applicant listed for this patent is DIC Corporation. Invention is credited to Taku Shimaya, Koji Tanaka, Masanori Uchigata, Yukihiko Yudate.
Application Number | 20180043602 15/557602 |
Document ID | / |
Family ID | 56978227 |
Filed Date | 2018-02-15 |
United States Patent
Application |
20180043602 |
Kind Code |
A1 |
Uchigata; Masanori ; et
al. |
February 15, 2018 |
LONG FIBER-REINFORCED POLYARYLENE SULFIDE RESIN MOLDED ARTICLE AND
METHOD FOR PRODUCING THE SAME
Abstract
To provide a polyarylene sulfide (PAS) resin composition and a
PAS resin molded article that are excellent in mechanical strengths
such as impact resistance while maintaining excellent heat
resistance of the PAS resin, and methods for producing the PAS
resin composition and the PAS resin molded article. Specifically,
provided are a method for producing a long fiber-reinforced PAS
resin molded article, the method including obtaining a long
fiber-reinforced PAS resin composition containing a PAS resin and a
fiber reinforcing material having a fiber length of more than 5 mm,
subsequently subjecting the resin composition and a PAS resin to
dry blending, and subsequently subjecting the dry-blended substance
to melting and subsequently to melt-molding; the long
fiber-reinforced PAS resin composition; and a method for producing
the long fiber-reinforced PAS resin composition.
Inventors: |
Uchigata; Masanori;
(Ichihara-shi, JP) ; Yudate; Yukihiko;
(Ichihara-shi, JP) ; Tanaka; Koji; (Ichihara-shi,
JP) ; Shimaya; Taku; (Ichihara-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DIC Corporation |
Tokyo |
|
JP |
|
|
Family ID: |
56978227 |
Appl. No.: |
15/557602 |
Filed: |
March 22, 2016 |
PCT Filed: |
March 22, 2016 |
PCT NO: |
PCT/JP2016/058961 |
371 Date: |
September 12, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29L 2023/22 20130101;
B29K 2081/04 20130101; B29K 2063/00 20130101; B29L 2022/00
20130101; B29L 2031/749 20130101; B29C 49/04 20130101; B29L
2031/3055 20130101; B29C 49/0005 20130101; B29K 2105/08 20130101;
C08L 63/00 20130101; B29B 13/04 20130101; B29B 7/30 20130101; B29B
13/02 20130101; C08J 5/04 20130101; B29K 2105/0088 20130101; C08J
2381/04 20130101; C08L 101/02 20130101; B29K 2309/08 20130101; B29B
7/002 20130101; B29B 7/7461 20130101; C08L 81/02 20130101; B29K
2995/0016 20130101; B29B 7/90 20130101; B29B 9/06 20130101; B29B
15/105 20130101; B29K 2105/12 20130101; B29B 7/02 20130101 |
International
Class: |
B29C 49/00 20060101
B29C049/00; B29B 15/10 20060101 B29B015/10; B29B 13/04 20060101
B29B013/04; B29B 7/00 20060101 B29B007/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 26, 2015 |
JP |
2015-064396 |
Apr 24, 2015 |
JP |
2015-089436 |
Claims
1. A method for producing a long fiber-reinforced polyarylene
sulfide resin molded article, the method being a method for
producing a blow-molded hollow article containing a polyarylene
sulfide resin and a fiber reinforcing material having a fiber
length of more than 5 mm, the method comprising subjecting a long
fiber-reinforced polyarylene sulfide resin composition containing a
polyarylene sulfide resin (a1) and a fiber reinforcing material
having a fiber length of more than 5 mm and a polyarylene sulfide
resin (a2) to dry blending, subsequently to heating at a
temperature not lower than a melting point of the polyarylene
sulfide resins to melt the polyarylene sulfide resins, and
subsequently to molding.
2. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein a
proportion of the long fiber-reinforced polyarylene sulfide resin
composition is 98 to 2 parts by mass and a proportion of the
polyarylene sulfide resin (a2) is 2 to 98 parts by mass, with
respect to the total 100 parts by mass of the long fiber-reinforced
polyarylene sulfide resin composition and the polyarylene sulfide
resin (a2).
3. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein, in the
long fiber-reinforced polyarylene sulfide resin composition, a
proportion of the polyarylene sulfide resin (a1) is 99 to 20 parts
by mass and a proportion of the fiber reinforcing material is 1 to
80 parts by mass, with respect to the total 100 parts by mass of
the polyarylene sulfide resin (a1) and the fiber reinforcing
material.
4. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the long
fiber-reinforced polyarylene sulfide resin composition is obtained
by coating or impregnating a continuous fiber with the polyarylene
sulfide resin (a1) that is melted and kneaded, subsequently cooling
the continuous fiber to obtain a strand, and cutting the strand to
a length of more than 5 mm.
5. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the
fiber reinforcing material has a fiber diameter of 5 to 50
.mu.m.
6. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the
fiber reinforcing material has an aspect ratio of 250 to 5000.
7. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the
fiber reinforcing material is at least one selected from the group
consisting of a glass fiber reinforcing material, a carbon fiber
reinforcing material, a basalt fiber reinforcing material, and an
aramid fiber reinforcing material.
8. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the
polyarylene sulfide resins have a non-Newtonian index of 0.9 to
1.2, and a melt viscosity at 300.degree. C. of 10 to 500 [Pas].
9. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the
molding is blow hollow molding, and the long fiber-reinforced
polyarylene sulfide resin molded article is a blow-molded hollow
article.
10. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the long
fiber-reinforced polyarylene sulfide resin composition contains, in
addition to the polyarylene sulfide resin and the fiber reinforcing
material having a fiber length of more than 5 mm, further a
thermoplastic elastomer (b1) optionally having at least one
functional group selected from the group consisting of an epoxy
group, an amino group, a carboxy group, an isocyanato group, and
moieties represented by a structural formula (1) below or a
structural formula (2) below ##STR00006## (where, in the structural
formula (1) and the structural formula (2), R's represent an alkyl
group having 1 to 8 carbon atoms).
11. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 10, wherein, in the
long fiber-reinforced polyarylene sulfide resin composition, a
proportion of the polyarylene sulfide resin (a1) is 98 to 19 parts
by mass, a proportion of the fiber reinforcing material is 1 to 79
parts by mass, and a proportion of the thermoplastic elastomer (b1)
is 1 to 30 parts by mass, with respect to the total 100 parts by
mass of the polyarylene sulfide resin (a1), the fiber reinforcing
material, and the thermoplastic elastomer (b1).
12. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 10, wherein the
long fiber-reinforced polyarylene sulfide resin composition is
obtained by coating or impregnating a continuous fiber with a
composition containing the polyarylene sulfide resin (a1) that is
melted and kneaded and the thermoplastic elastomer (b1),
subsequently cooling the continuous fiber to obtain a strand, and
cutting the strand to a length of more than 5 mm.
13. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the long
fiber-reinforced polyarylene sulfide resin composition is
dry-blended with the polyarylene sulfide resin (a2) and further a
thermoplastic elastomer (b2) optionally having at least one
functional group selected from the group consisting of an epoxy
group, an amino group, a carboxy group, an isocyanato group, and
moieties represented by a structural formula (1) below or a
structural formula (2) below ##STR00007## (where, in the structural
formula (1) and the structural formula (2), R's represent an alkyl
group having 1 to 8 carbon atoms).
14. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 13, wherein a
proportion of the long fiber-reinforced polyarylene sulfide resin
composition is 98 to 2 parts by mass, and a total proportion of the
polyarylene sulfide resin (a2) and the thermoplastic elastomer (b2)
is 2 to 98 parts by mass, with respect to the total 100 parts by
mass of the long fiber-reinforced polyarylene sulfide resin
composition, the polyarylene sulfide resin (a2), and the
thermoplastic elastomer (b2).
15. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 13, wherein a
proportion of the polyarylene sulfide resin (a2) is 99.9 to 50
parts by mass and a proportion of the thermoplastic elastomer (b2)
is 0.1 to 50 parts by mass, with respect to the total 100 parts by
mass of the polyarylene sulfide resin (a2) and the thermoplastic
elastomer (b2).
16. The method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to claim 1, wherein the long
fiber-reinforced polyarylene sulfide resin composition is provided
as a pellet, and the fiber reinforcing material has a length not
less than a length of the pellet.
17. A long fiber-reinforced polyarylene sulfide resin molded
article comprising a polyarylene sulfide resin and a fiber
reinforcing material having a fiber length of more than 5 mm,
wherein a MFR measured with a melt indexer at a cylinder
temperature of 316.degree. C. with an orifice diameter of 3 mm is
10 to 100 [g/10 min], and a proportion of the polyarylene sulfide
resin is 99 to 25 parts by mass, and a proportion of the fiber
reinforcing material is 1 to 75 parts by mass, with respect to the
total 100 parts by mass of the polyarylene sulfide resin and the
fiber reinforcing material.
18. The long fiber-reinforced polyarylene sulfide resin molded
article according to claim 17, wherein the long fiber-reinforced
polyarylene sulfide resin molded article contains, in addition to
the polyarylene sulfide resin and the fiber reinforcing material
having a fiber length of more than 5 mm, further a thermoplastic
elastomer optionally having at least one functional group selected
from the group consisting of an epoxy group, an amino group, a
carboxy group, an isocyanato group, and moieties represented by a
structural formula (1) below or a structural formula (2) below
##STR00008## (where, in the structural formula (1) and the
structural formula (2), R's represent an alkyl group having 1 to 8
carbon atoms), and a proportion of the polyarylene sulfide resin is
98 to 24 parts by mass, a proportion of the fiber reinforcing
material is 1 to 74 parts by mass, and a proportion of the
thermoplastic elastomer is 0.1 to 30 parts by mass, with respect to
the total 100 parts by mass of the polyarylene sulfide resin, the
fiber reinforcing material, and the thermoplastic elastomer.
Description
TECHNICAL FIELD
[0001] The present invention relates to a long fiber-reinforced
polyarylene sulfide resin composition, its molded article, and
methods for producing the resin composition and the molded article,
in particular, to a blow-molded hollow article and a method for
producing the molded article.
BACKGROUND ART
[0002] With the recent trend toward a decrease in the fuel
consumption of automobiles for the purpose of saving of resources,
energy conservation, and a decrease in emission of carbon dioxide,
there has particularly been a demand for a decrease in the weight
of automobile parts.
[0003] Conventionally, in order to decrease the weight of various
materials formed of metal, the metal has been replaced by resin
materials having a lower specific gravity than the metal, in
particular, polyamide-based materials. However, polyamide-based
materials have lower heat resistance, compared with metal
materials. For this reason, polyamide-based materials are limited
for their usage. Thus, there has been a demand for a resin material
having higher heat resistance.
[0004] In particular, regarding automobile parts that are ducts
within engine rooms, conventional aluminum materials have been
replaced by blow-molded hollow articles formed of resin materials.
Currently, polyamide-based materials are mainly used. However,
since the members are mainly exposed to exhaust gas,
polyamide-based materials are insufficient in terms of heat
resistance. For this reason, there has been a demand for a blow
hollow molding material that has high heat resistance and also has
chemical resistance and impact resistance.
[0005] Thus, use of an engineering plastic excellent in terms of
heat resistance, chemical resistance, flame resistance, electrical
characteristics, and the like, a polyarylene sulfide resin
(hereafter, sometimes abbreviated as a PAS resin), has been studied
not only for automobile parts but also for various applications
including electrical or electronic components and precision
machinery components. However, molded articles formed of the
polyarylene sulfide resin are known to be brittle. Although such
molded articles are provided so as to have impact resistance by
addition of various fillers, they are still insufficient as
replacements for metal materials.
[0006] In particular, various attempts have been made for a long
time for use of blow hollow molding materials using a polyarylene
sulfide resin. However, when molding a polyarylene sulfide resin,
it has extremely high melt fluidity, and thus in normal extrusion
blow molding, that is, in a method of extruding and blow-molding a
parison, there is a problem in that draw-down of the parison
extremely increases, and it is very difficult to mold the parison
into a container having small thickness unevenness. Accordingly,
the use of the polyarylene sulfide resin is mostly limited to an
injection molding method, and most of the molded articles of the
polyarylene sulfide resin have small sizes. The application of the
polyarylene sulfide resin to large-sized components such as bottles
and tanks provided by blow molding or the like has been rarely
performed.
[0007] As an example of the application of the polyarylene sulfide
resin to blow molding, there is a known resin composition obtained
by melting and kneading a polyarylene sulfide resin and an epoxy
group-containing olefin-based copolymer (PTL 1). However, although
the polyarylene sulfide resin has a high melt viscosity, it has a
high proportion of terminal carboxy groups, and contains a large
amount of low-molecular-weight components. For this reason, there
is room to improve moldability of the composition in terms of
draw-down resistance and thickness unevenness in performing the
blow hollow molding. In addition, there is also room to improve the
mechanical strengths, particularly, thermal shock resistance
particularly because of a high proportion of the reaction products
between the low-molecular-weight components of the polyarylene
sulfide resin and the epoxy group-containing olefin-based
copolymer. Thus, the composition has not yet been used under more
harsh environments such as in regions including automobile
engines.
[0008] There is a known blow-molded hollow article excellent in
moldability and mechanical strengths such as thermal shock
resistance, which is provided by the combination of a
high-molecular-weight linear polyarylene sulfide resin having a
specified concentration of terminal carboxy groups and an
olefin-based polymer (PTL 2). However, while use of the
olefin-based polymer can impart mechanical strengths such as impact
resistance to blow-molded hollow articles containing the
polyarylene sulfide resin, it also causes degradation of the heat
resistance. For this reason, there has been a demand for a
blow-molded hollow article that is excellent in mechanical
strengths such as impact resistance while maintaining excellent
heat resistance of a polyarylene sulfide resin.
CITATION LIST
Patent Literature
[0009] PTL 1: Japanese Unexamined Patent Application Publication
No. 3-236930
[0010] PTL 2: WO2001/148929 Pamphlet
SUMMARY OF INVENTION
Technical Problem
[0011] Accordingly, an object of the present invention is to
provide a polyarylene sulfide resin molded article that is
excellent in mechanical strengths such as impact resistance while
maintaining excellent heat resistance of the polyarylene sulfide
resin; a polyarylene sulfide resin composition for providing the
molded article; and methods for producing the molded article and
the resin composition. Another object is to provide, particularly
among molded articles, a blow-molded hollow article that is
excellent in mechanical strengths such as impact resistance and is
also excellent in moldability in terms of draw-down resistance,
thickness unevenness, and inner-surface smoothness; a polyarylene
sulfide resin composition for providing the molded article; and
methods for producing the molded article and the resin
composition.
Solution to Problem
[0012] The inventors of the present invention have conducted
intensive studies to solve the above-described problems, and as a
result, have found that it is possible to provide a long
fiber-reinforced polyarylene sulfide resin molded article that is
excellent in mechanical strengths such as impact resistance by
subjecting a long fiber-reinforced polyarylene sulfide resin
composition containing a polyarylene sulfide resin and a fiber
reinforcing material having a fiber length of more than 5 mm, and a
polyarylene sulfide resin to dry blending, and by subsequently
melting and then molding the dry-blended substance. Thus, the
inventors have completed the present invention.
[0013] Specifically, the present invention relates to a method for
producing a long fiber-reinforced polyarylene sulfide resin molded
article, the method being a method for producing a blow-molded
hollow article containing a polyarylene sulfide resin and a fiber
reinforcing material having a fiber length of more than 5 mm,
[0014] the method including subjecting a long fiber-reinforced
polyarylene sulfide resin composition containing a polyarylene
sulfide resin (a1) and a fiber reinforcing material having a fiber
length of more than 5 mm and a polyarylene sulfide resin (a2) to
dry blending, subsequently to heating at a temperature not lower
than a melting point of the polyarylene sulfide resins to melt the
polyarylene sulfide resins, and subsequently to molding.
[0015] The present invention also relates to a long
fiber-reinforced polyarylene sulfide resin molded article including
a polyarylene sulfide resin and a fiber reinforcing material having
a fiber length of more than 5 mm,
[0016] wherein a MFR measured with a melt indexer at a cylinder
temperature of 316.degree. C. with an orifice diameter of 3 mm is
10 to 100 [g/10 min], and
[0017] a proportion of the polyarylene sulfide resin is 99 to 25
parts by mass, and a proportion of the fiber reinforcing material
is 1 to 75 parts by mass, with respect to the total 100 parts by
mass of the polyarylene sulfide resin and the fiber reinforcing
material.
Advantageous Effects of Invention
[0018] According to the present invention, it is possible to
provide a polyarylene sulfide resin molded article that is
excellent in mechanical strengths such as impact resistance while
maintaining excellent heat resistance of the polyarylene sulfide
resin; a polyarylene sulfide resin composition for providing the
molded article; and methods for producing the molded article and
the resin composition. It is also possible to provide, particularly
among molded articles, a blow-molded hollow article that is
excellent in mechanical strengths such as impact resistance and is
also excellent in moldability in terms of draw-down resistance,
thickness unevenness, and inner-surface smoothness; a polyarylene
sulfide resin composition for providing the molded article; and
methods for producing the molded article and the resin
composition.
DESCRIPTION OF EMBODIMENTS
[0019] A method for producing a long fiber-reinforced polyarylene
sulfide resin molded article according to the present invention is
a method for producing a long fiber-reinforced polyarylene sulfide
resin molded article containing a polyarylene sulfide resin and a
fiber reinforcing material having a fiber length of more than 5
mm,
[0020] the method including subjecting a long fiber-reinforced
polyarylene sulfide resin composition containing a polyarylene
sulfide resin (a) and a fiber reinforcing material having a fiber
length of more than 5 mm and a polyarylene sulfide resin (b) to dry
blending, subsequently to heating at a temperature not lower than a
melting point of the polyarylene sulfide resins to melt the
polyarylene sulfide resins, and subsequently to molding.
[0021] A long fiber-reinforced polyarylene sulfide resin
composition used in the present invention will be described.
[0022] A polyarylene sulfide resin used in the present invention
has a resin structure having, as a repeating unit, a structure
formed by bonding an aromatic ring and a sulfur atom. Specifically,
the polyarylene sulfide resin is a resin having, as repeating
units, a structure part represented by the following Formula
(1)
##STR00001##
(in the formula, R.sup.1 and R.sup.2 are each independently a
hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro
group, an amino group, a phenyl group, a methoxy group, or an
ethoxy group), and optionally a trifunctional structure part
represented by the following Formula (2).
##STR00002##
[0023] The amount of the trifunctional structure part represented
by the following Formula (8) is preferably 0.001 to 3 mol %, and
particularly preferably 0.01 to 1 mol % with respect to the total
number of moles of the trifunctional structure part and the other
structure parts.
[0024] Here, in the structure part represented by the above Formula
(1), in particular, R.sup.1 and R.sup.2 in the formula are
preferably hydrogen atoms in view of the mechanical strength of the
polyarylene sulfide resin (A). In that case, examples of the
structure part include a structure part formed by bonding at a para
position represented by the following Formula (3) and a structure
part formed by bonding at a meta position represented by the
following Formula (4).
##STR00003##
[0025] Of these, particularly, in the repeating unit, regarding the
bonding of the sulfur atom to the aromatic ring, preferred is a
structure formed by bonding at the para position represented by the
above structural Formula (3) in view of the heat resistance and the
crystallinity of the polyarylene sulfide resin.
[0026] The polyarylene sulfide resin may include, not only the
structure parts represented by the above Formulae (1) and (2), but
also structure parts represented by the following Structural
Formulae (5) to (8) such that the amounts of the structure parts
represented by Structural Formulae (5) to (8) are not more than 30
mol % of the total amount of the structure parts represented by the
above Formulae (1) and (2).
##STR00004##
[0027] Particularly, in the present invention, the amounts of the
structure parts represented by the above Formulae (5) to (8) are
preferably 10 mol % or less in view of the heat resistance and the
mechanical strength of the polyarylene sulfide resin. When the
polyarylene sulfide resin includes structure parts represented by
the above Formulae (5) to (8), the bonding form thereof may form a
random copolymer or a block copolymer.
[0028] The polyarylene sulfide resin may have, in its molecular
structure, a naphthyl sulfide bond, for example. The amount of the
naphthyl sulfide bond is preferably not more than 3 mol %, and
particularly preferably not more than 1 mol %, with respect to the
total number of moles of the naphthyl sulfide bond and the other
structure parts.
[0029] The method for producing the polyarylene sulfide resin is
not particularly limited. However, examples thereof include 1) a
method of polymerizing a dihalogeno aromatic compound, if
necessary, with the addition of a polyhalogeno aromatic compound or
other copolymerization components, in the presence of sulfur and
sodium carbonate, 2) a method of polymerizing a dihalogeno aromatic
compound, if necessary, with the addition of a polyhalogeno
aromatic compound or other copolymerization components, in the
presence of a sulfidizing agent or the like in a polar solvent, and
3) a method of self-condensing p-chlorothiophenol, if necessary,
with the addition of other copolymerization components. Among these
methods, the method described in 2) is versatile and preferred.
During the reaction, an alkali metal salt of a carboxylic acid or a
sulfonic acid, or an alkali hydroxide may be added in order to
adjust the degree of polymerization. Particularly preferred are
polyarylene sulfide resins obtained by, of such methods described
in 2), a method of producing a polyarylene sulfide resin, the
method including introducing an aqueous sulfidizing agent into a
heated mixture containing an organic polar solvent and a dihalogeno
aromatic compound at a rate at which water can be removed from the
reaction mixture to react the dihalogeno aromatic compound with the
sulfidizing agent in the organic polar solvent, if necessary, with
the addition of a polyhalogeno aromatic compound, and controlling
the water content in the reaction system to be in a range of 0.02
to 0.5 moles with respect to 1 mole of the organic polar solvent
(refer to Japanese Unexamined Patent Application Publication No.
07-228699); or by a method of reacting, in the presence of a solid
alkali metal sulfide and an aprotic polar organic solvent, a
dihalogeno aromatic compound, (if necessary, with the addition of a
polyhalogeno aromatic compound or other copolymerization
components,) an alkali metal hydrosulfide, and an organic acid
alkali metal salt, wherein the amount of the organic acid alkali
metal salt is 0.01 to 0.9 moles with respect to 1 mole of the
sulfur source and the water content in the reaction system is
controlled to be 0.02 moles or less with respect to 1 mole of the
aprotic polar organic solvent (refer to WO2010/058713 Pamphlet).
Specific examples of the dihalogeno aromatic compound include
p-dihalobenzene, m-dihalobenzene, o-dihalobenzene,
2,5-dihalotoluene, 1,4-dihalonaphthalene,
1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic
acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene,
2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p'-dihalodiphenyl
ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone,
4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and a
compound having an alkyl group having 1 to 18 carbon atoms on the
aromatic ring of each of the above compounds. Examples of the
polyhalogeno aromatic compound include 1,2,3-trihalobenzene,
1,2,4-trihalobenzene, 1,3,5-trihalobenzene,
1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, and
1,4,6-trihalonaphthalene. The halogen atoms contained in the above
compounds are desirably chlorine atoms or bromine atoms.
[0030] The method of post-treating the reaction mixture containing
the polyarylene sulfide resin obtained by the polymerization
process is not particularly limited. However, examples thereof
include (1) a method including: after the completion of the
polymerization reaction, distilling away the solvent from the
reaction mixture under reduced pressure or ordinary pressure after
addition or no addition of an acid or a base, and subjecting the
solids after the distillation of the solvent to rinsing with a
solvent one or more times, such as water, a reaction solvent (or an
organic solvent having a capability of dissolving low-molecular
polymers, the capability being equivalent to that of the reaction
solvent), acetone, methyl ethyl ketone, or an alcohol, and further
to neutralization, rinsing with water, filtering, and drying; (2) a
method including: after the completion of the polymerization
reaction, adding to the reaction mixture, as a precipitation agent,
a solvent (which is soluble in the polymerization solvent having
been used, and also serves as a poor solvent at least for the
polyarylene sulfide) such as water, acetone, methyl ethyl ketone,
an alcohol, an ether, halogenated hydrocarbon, aromatic
hydrocarbon, or aliphatic hydrocarbon to precipitate solid products
of the polyarylene sulfide, inorganic salts, and the like, and
subjecting the solid products to filtering, rinsing, and drying;
(3) a method including: after the completion of the polymerization
reaction, adding to the reaction mixture a reaction solvent (or an
organic solvent having a capability of dissolving low-molecular
polymers, the capability being equivalent to that of the reaction
solvent), subjecting the reaction mixture to stirring, subsequently
to filtering to remove low-molecular-weight polymers, subsequently
to rinsing one or more times with a solvent such as water, acetone,
methyl ethyl ketone, or an alcohol, subsequently to neutralization,
rising with water, filtering, and drying; (4) a method including:
after the completion of the polymerization reaction, adding water
to the reaction mixture to subject the reaction mixture to rinsing
with water and filtering, to an acid treatment with an acid added
during the rinsing with water as necessary, and to drying; and (5)
a method including: after the completion of the polymerization
reaction, subjecting the reaction mixture to filtering, rinsing
with a reaction solvent one or more times as necessary, further to
rinsing with water, filtering, and drying.
[0031] Incidentally, in the post-treatment methods exemplified in
(1) to (5) above, the polyarylene sulfide resin may be dried in
vacuum, air, or an inert gas atmosphere such as nitrogen.
[0032] The melt viscosity of the polyarylene sulfide resin is not
particularly limited as long as it is in a suitable range for blow
molding. However, the melt viscosity at a temperature of
300.degree. C. and a shear rate of 10 sec.sup.-1 is preferably 10
to 500 Pas, more preferably 25 to 300 Pas, and still more
preferably 45 to 200 Pas. When the melt viscosity is 10 Pas or
higher, draw-down is less likely to occur. On the other hand, when
the melt viscosity is 500 Pas or lower, the stability in extruding
a parison is good, and a uniform molded article without thickness
unevenness is likely to be obtained.
[0033] The non-Newtonian index of the polyarylene sulfide resin is
not particularly limited as long as it is in a suitable range for
blow molding. However, the non-Newtonian index is preferably 0.9 to
1.2.
[0034] In summary, regarding a polyarylene sulfide resin used in
the present invention, when the polyarylene sulfide resin itself
has a high melt viscosity suitable for blow hollow molding and also
has, among linear structures, a straight-chain structure that has a
low branching degree in which the non-Newtonian index is 0.9 to
1.2, it is possible to prevent an excessive increase in the melt
viscosity of the melted and kneaded material due to reaction with
the fiber reinforcing material, to thereby exhibit excellent
moldability without thickness unevenness. Thus, improvements tend
to be achieved in mechanical strengths of a blow-molded hollow
article, in particular, impact resistance.
[0035] Incidentally, in a method for producing a long
fiber-reinforced polyarylene sulfide resin molded article according
to the present invention, the polyarylene sulfide resin (sometimes
referred to as the "polyarylene sulfide resin (a1)") contained in
the long fiber-reinforced polyarylene sulfide resin composition,
and the polyarylene sulfide resin (sometimes referred to as the
"polyarylene sulfide resin (a2)") to be dry-blended with the long
fiber-reinforced polyarylene sulfide resin composition may be the
same or different as long as these resins fall within the
above-described definitions of polyarylene sulfide resin.
[0036] As a fiber reinforcing material used in the present
invention, a known inorganic fiber reinforcing material or a known
organic fiber reinforcing material can be used. Examples thereof
include glass fiber reinforcing materials, metal fiber reinforcing
materials, basalt fiber reinforcing materials, carbon fiber
reinforcing materials, aramid fiber (wholly aromatic polyamide
fiber) reinforcing materials, nylon MXD6 fiber (fiber formed of
copolycondensation polymer of m-xylylenediamine and adipic acid)
reinforcing materials, PET fiber reinforcing materials, PBT fiber
reinforcing materials, and wholly aromatic polyester fiber (Kevlar
fiber) reinforcing materials.
[0037] These fiber reinforcing materials can be used not only in
the form of a monofilament, but also in the form of a roving in
which a large number of monofilaments are bundled with a sizing
agent. The roving is preferably a roving that is a bundle of 500 to
60,000 monofilaments having an average fiber diameter of 5 to 50
.mu.m, preferably an average fiber diameter of 6 to 30 .mu.m, and
more preferably a roving that is a bundle of 1,000 to 20,000
monofilaments having an average fiber diameter of 9 to 24 .mu.m.
Such rovings can also be used in the form of multiple wound yarn of
two or more rovings. Such rovings themselves twisted can also be
used. Examples of the sizing agent include sizing agents containing
one or more kinds selected from maleic anhydride-based compounds,
urethane-based compounds, acrylic compounds, epoxy-based compounds,
and copolymers of the foregoing compounds; and preferred examples
of the sizing agents include those containing an epoxy-based
compound or a urethane-based compound. Among these, preferred
examples are epoxy-based compounds and urethane-based compounds,
and more preferred examples are epoxy-based compounds. Examples of
the epoxy-based compounds include bisphenol-epichlorohydrin-type
epoxy resins, glycidyl ether-type epoxy resins, tetraepoxy resins,
novolac-type epoxy resins, glycidylamine, epoxy alkyl esters, and
epoxidized unsaturated compounds. Examples of the urethane-based
compounds include compounds synthesized from an isocyanate such as
m-xylylene diisocyanate (XDI), 4,4'-methylenebis(cyclohexyl
isocyanate) (HMDI), or isophorone diisocyanate (IPDI), and a
polyester- or polyether-based diol.
[0038] In the present invention, a thermoplastic elastomer can be
optionally used. The thermoplastic elastomer that can be optionally
used is preferably a thermoplastic elastomer having at least one
functional group selected from the group consisting of an epoxy
group, an amino group, a carboxy group, an isocyanato group, and
moieties represented by a structural formula (1) or a structural
formula (2) below
##STR00005##
[0039] (where, in the structural formula (1) and the structural
formula (2), R's represent an alkyl group having 1 to 8 carbon
atoms). These groups and moieties are functional groups that are
highly miscible with carboxy groups or functional groups that are
reactive to carboxy groups. Thus, when the elastomer is melted and
kneaded with a polyarylene sulfide resin having a carboxy group,
the elastomer and the resin sufficiently dissolve in or react with
each other. As a result, a molded article according to the present
invention can have mechanical strengths, in particular, excellent
bending strength, high impact resistance, and a high modulus of
elasticity in bending, which is preferable.
[0040] The thermoplastic elastomer is preferably, for example, a
polyolefin obtained by copolymerizing an .alpha.-olefin and a
monomer such as a vinyl polymerizable compound that may have the
above-described functional group. Examples of the .alpha.-olefin
include .alpha.-olefins having 2 to 8 carbon atoms such as
ethylene, propylene, and butene-1. Examples of the vinyl
polymerizable compound that may have the above-described functional
group include .alpha.,.beta.-unsaturated carboxylic acids and alkyl
esters thereof such as (meth)acrylic acid and (meth)acrylate; and
.alpha.,.beta.-unsaturated dicarboxylic acids and derivatives
thereof such as unsaturated dicarboxylic acids having 4 to 10
carbon atoms such as maleic acid, fumaric acid, and itaconic acid,
mono- or di-esters of the foregoing, and acid anhydrides of the
foregoing.
[0041] More specifically, for example, the polyolefin having an
epoxy group is not particularly limited as long as it is an
olefin-based polymer having an epoxy group; however, the polyolefin
is preferably a copolymer of an .alpha.-olefin and a glycidyl ester
of an .alpha.,.beta.-unsaturated acid. Examples of the
.alpha.-olefin include ethylene, propylene, and butene-1. Specific
examples of the glycidyl ester of an .alpha.,.beta.-unsaturated
acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl
ethacrylate. The modification ratio of the monomer components to
the .alpha.-olefin is not particularly limited; however, the
modification ratio represented as a ratio of the mass of the
monomers having the modified portions in the copolymer to 100 mass
of the copolymer, is preferably 0.1 to 15 parts by mass, in
particular, preferably 0.5 to 10 parts by mass.
[0042] The polyolefin having an amino group or an isocyanato group
can be obtained by, for example, causing a polyamine or a
polyisocyanate such as an alkylene diamine or an alkylene
diisocyanate to react with the above-described polyolefin modified
with a carboxylic acid. Examples of the alkylene diamine and the
alkylene diamine include ethylenediamine, pentamethylenediamine,
hexamethylenediamine, ethylene diisocyanate, pentamethylene
diisocyanate, and hexamethylene diisocyanate.
[0043] An olefin-based polymer that does not have a functional
group reactive to a carboxy group, what is called, an unmodified
olefin-based polymer can also be used. Examples thereof include
homopolymers such as polyethylene, polypropylene, polystyrene,
polyacrylate, polymethacrylate, poly-1-butene, poly-1-pentene, and
polymethylpentene; and ethylene-.alpha.-olefin copolymers. Of
these, the ethylene-.alpha.-olefin copolymers are preferred.
[0044] Such an ethylene-.alpha.-olefin copolymer is a copolymer
that has, as constitutional components, ethylene and at least one
.alpha.-olefin having 3 to 20 carbon atoms. Specific examples of
the .alpha.-olefin having 3 to 20 carbon atoms include propylene,
1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,
1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene,
1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,
3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene,
4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,
3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene,
12-ethyl-1-tetradecene, and combinations of the foregoing. Of these
.alpha.-olefins, .alpha.-olefins having 6 to 12 carbon atoms are
more preferably used because the resultant copolymer has enhanced
mechanical strength and further enhanced modification effects.
[0045] When a polyolefin that does not have a functional group,
what is called, an unmodified polyolefin is used, its melt
viscosity is not particularly limited; however, the melt viscosity
measured as a melt flow rate (temperature: 190.degree. C., load:
2.16 kg) is preferably 0.01 to 70 poises.
[0046] Incidentally, the olefin-based polymer may be obtained by
copolymerization with, for example, another olefin-based monomer
such as methyl acrylate, methyl methacrylate, acrylonitrile,
styrene, vinyl acetate, or vinyl ether as long as advantageous
effects provided by the present invention are not impaired.
[0047] A thermoplastic elastomer that can be used in the present
invention is preferably an elastomer that can be melted and
dispersed by mixing at a kneading temperature for the polyarylene
sulfide resin. In view of this, an elastomer is more preferred that
has a melting point of 300.degree. C. or less and has rubber
elasticity at room temperature. In particular, in the case of
considering heat resistance, ease of mixing, and enhancement of
freezing resistance, an elastomer having a glass transition
temperature of -30.degree. C. or less is preferred because it has
rubber elasticity even at very low temperatures. The lower the
glass transition temperature, the more preferable it is from the
viewpoint of enhancing freezing resistance. However, in general,
the glass transition temperature is preferably -180.degree. C. to
-30.degree. C., particularly preferably -150.degree. C. to
-30.degree. C.
[0048] The above-described polyolefins having a functional group
having high miscibility with a carboxy group or a functional group
reactive to a carboxy group, and the above-described polyolefins
not having the functional groups, what is called, unmodified
polyolefins can be used alone or in combination of two or more
thereof.
[0049] Incidentally, in a method for producing a long
fiber-reinforced polyarylene sulfide resin molded article according
to the present invention, to the long fiber-reinforced polyarylene
sulfide resin composition, the thermoplastic elastomer (sometimes
referred to as the "thermoplastic elastomer (b1)") may be added;
and/or, as a component dry-blended with the long fiber-reinforced
polyarylene sulfide resin composition, the thermoplastic elastomer
(sometimes referred to as the "thermoplastic elastomer (b2)") may
be further added to the polyarylene sulfide resin (a2).
[0050] A long fiber-reinforced polyarylene sulfide resin
composition used in the present invention contains a polyarylene
sulfide resin and a fiber reinforcing material having a fiber
length of more than 5 mm. The long fiber-reinforced polyarylene
sulfide resin composition can be produced on the basis of methods
such as the method described in Japanese Unexamined Patent
Application Publication No. 2003-192911. For example, a strand
obtained by coating or impregnating a continuous fiber
(monofilament or roving) with a melted polyarylene sulfide resin
and then cooling the resulting continuous fiber, is cut to a length
of more than 5 mm, and thus the long fiber-reinforced polyarylene
sulfide resin composition can be obtained. In this case, to the
melted polyarylene sulfide resin, for example, the thermoplastic
elastomer, a processing stabilizer, an oxidation stabilizer, a
molding aid, or other additives may be added as necessary.
[0051] In the course of preparing a long fiber-reinforced
polyarylene sulfide resin composition according to the present
invention, a polyarylene sulfide resin serving as a base resin is
put after, as necessary, blending with, for example, the
thermoplastic elastomer, a processing stabilizer, an oxidation
stabilizer, a molding aid, filler, or other additives, into a
single- or twin-screw extruder having a heating mechanism, and then
melted and kneaded at a temperature not lower than the melting
point of the polyarylene sulfide resin, preferably at a temperature
not lower than the melting point+10.degree. C., more preferably at
a temperature in a range of the melting point+10.degree. C. to the
melting point+100.degree. C., and still more preferably at a
temperature in a range of the melting point+20.degree. C. to the
melting point+50.degree. C., to shift into a flowable state. After
that, the resulting material is charged into an impregnation
apparatus (impregnation die) at a predetermined speed.
[0052] As the impregnation apparatus, an opening impregnation
apparatus is used in a case where the continuous fiber is a roving.
The opening impregnation apparatus includes a melted resin storing
portion, a fiber guide hole (inlet) formed in the upstream-side
boundary wall or the upstream-side top board, and a shaping nozzle
formed in the downstream-side boundary wall. In the apparatus, two
or more opening pins (fixed so as not to rotate regardless of the
movement of long fibers) or opening rolls (which can automatically
or associatively rotate with the movement of long fibers) are
systemically mounted toward the downstream side so as to extend
across the right and left walls and so as to be fixed to or be
rotatable (turnable) on the two walls. Incidentally, the opening
pins or opening rolls may be mounted so as to form upper and lower
rows (two or more rows) with a predetermined gap therebetween, for
example. In the opening impregnation apparatus, by guiding a
continuous fiber to the melted resin and moving it around the
opening pins or opening rolls in zigzags, or by passing the
continuous fiber through an intermediate region between two opening
pins so as not to come into contact with any of these two opening
pins installed as upper and lower pins so as to be separated from
each other with a predetermined gap width therebetween, opening the
roving and coating or impregnating the opened fibers with the
melted resin may be performed.
[0053] Subsequently, a strand-like material extruded from the
impregnation apparatus is cooled to a temperature lower than the
melting temperature of the polyarylene sulfide resin, preferably to
a room temperature (23.degree. C.), and thus a strand formed by
pultrusion-molding an endless fiber is obtained. In this case, the
fiber reinforcing material or roving may be twisted. For example,
plural, preferably 2 to 30, continuous fiber reinforcing materials
or rovings may be passed through the impregnation apparatus, and
the plural fiber reinforcing materials or rovings may be wound up
while being twisted, to form a single strand. A long
fiber-reinforced polyarylene sulfide resin composition according to
the present invention is obtained as columnar pellets by cutting
the obtained strand to a length of more than 5 mm, preferably more
than 5 mm and 30 mm or less, more preferably 6 mm or more and 20 mm
or less, and still more preferably 6 mm or more and 15 mm or less.
Incidentally, the pellet diameter and the pellet length are not
particularly limited as long as advantageous effects provided by
the present invention are not impaired; the pellet diameter is
preferably set to 1.0 to 6.0 mm, more preferably 1.5 to 4.0 mm. The
pellet length is the same as the length to which the strand is
cut.
[0054] The fiber reinforcing material obtained in this manner has
an aspect ratio of 250 to 5000, preferably 600 to 4000, still more
preferably 800 to 3000. To the fiber reinforcing material having a
fiber length of more than 5 mm, a fiber reinforcing material having
a fiber length of 5 mm or less may be added. Also in this case, the
number-average aspect ratio is preferably adjusted to be 120 to
3000 from the viewpoint of maintaining advantageous effects
provided by the invention.
[0055] Since the long fiber-reinforced polyarylene sulfide resin
composition obtained in this manner is provided as the columnar
pellets obtained by cutting the strand formed by pultrusion-molding
an endless fiber, the fiber length of the fiber reinforcing
material in such a pellet is equal to or larger than the length of
the pellet. In the case of using such fibers having a large fiber
length, the long fibers are physically entangled in the parison
during melt molding, in particular, blow molding, and therefore,
draw-down properties can be improved. Furthermore, in the case of
applying, to the surfaces of the fibers, a sizing agent having
reactivity for enhancing the interaction with the resin, adhesion
of the fibers to the polyarylene sulfide resin is enhanced. This
results in stronger adhesion at the interface between the fibers
and the resin, so that draw-down properties can be improved. In
addition, by using fibers having a large fiber length, mechanical
properties, in particular, impact resistance can be improved.
[0056] Incidentally, in the long fiber-reinforced polyarylene
sulfide resin composition, the proportions of the polyarylene
sulfide resin (a1), the fiber reinforcing material, and the
thermoplastic elastomer (b1), which is used as necessary, are not
particularly limited as long as advantageous effects provided by
the present invention are not impaired. However, the proportions
may be as follows.
[0057] Specifically, with respect to the total 100 parts by mass of
the polyarylene sulfide resin (a1) and the fiber reinforcing
material, the proportion of the polyarylene sulfide resin (a1) is
preferably 99 to 20 parts by mass, and the proportion of the fiber
reinforcing material is 1 to 80 parts by mass; more preferably, the
proportion of the polyarylene sulfide resin (a1) is 95 to 30 parts
by mass, and the proportion of the fiber reinforcing material is 5
to 70 parts by mass. By employing such blending proportions, a
molded article tends to be obtained that has excellent melt
moldability, and has excellent mechanical properties represented by
heat resistance, chemical resistance, and impact resistance; in
particular, draw-down of the parison is less likely to occur during
blow hollow molding and thus good blow moldability is exhibited,
and a blow-molded hollow article that is excellent in heat
resistance and chemical resistance tends to be obtained.
[0058] When the thermoplastic elastomer is further added to the
long fiber-reinforced polyarylene sulfide resin composition, with
respect to the total 100 parts by mass of the polyarylene sulfide
resin (a1), the fiber reinforcing material, and the thermoplastic
elastomer (b1), the proportion of the polyarylene sulfide resin
(a1) is preferably 98 to 19 parts by mass, the proportion of the
fiber reinforcing material is preferably 1 to 79 parts by mass, and
the proportion of the thermoplastic elastomer (b1) is preferably 1
to 30 parts by mass; more preferably, the proportion of the
polyarylene sulfide resin (a1) is 94 to 29 parts by mass, the
proportion of the fiber reinforcing material is 5 to 69 parts by
mass, and the proportion of the thermoplastic elastomer (b1) is 1
to 20 parts by mass. By employing such blending proportions, a
molded article tends to be obtained that has excellent melt
moldability, and has more excellent mechanical properties
represented by heat resistance, chemical resistance, and, in
particular, impact resistance; furthermore, the composition is
suitable for a blow-molded hollow article, and draw-down of the
parison is less likely to occur during blow hollow molding and thus
good blow moldability is exhibited, and a blow-molded hollow
article tends to be obtained that has excellent mechanical
properties represented by heat resistance, chemical resistance,
and, in particular, impact resistance.
[0059] A long fiber-reinforced polyarylene sulfide resin
composition used in the present invention may further contain
various fillers in order to further improve performances such as
strength, heat resistance, and dimensional stability as long as
advantageous effects provided by the present invention are not
impaired. As such fillers, known conventional materials can be used
as long as advantageous effects provided by the present invention
are not impaired, and examples thereof include fillers having
various forms such as a granular form and a fibrous form.
Specifically, fibrous fillers can be used that have a fiber length
of less than 6 mm, such as fibers, e.g., glass fibers, carbon
fibers, ceramic fibers, aramid fibers, metal fibers, potassium
titanate, silicon carbide, calcium sulfate, and calcium silicate,
and natural fibers, e.g., wollastonite. Other examples include
barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite,
sericite, zeolite, mica, isinglass, talc, attapulgite, ferrite,
calcium silicate, calcium carbonate, magnesium carbonate, and glass
beads. Such fillers used in the present invention are not essential
components. However, the fillers are preferably added in an amount
of more than 0 parts by mass, and generally in an amount of 10
parts by mass or more and 500 parts by mass or less with respect to
100 parts by mass of the polyarylene sulfide resin because various
performances such as strength, stiffness, heat resistance, heat
dissipation properties, or dimensional stability can be improved
depending on the purpose of the fillers added.
[0060] In addition, a long fiber-reinforced polyarylene sulfide
resin composition used in the present invention may contain known
additives as long as advantageous effects provided by the present
invention are not impaired. Examples of such known additives
include mold release agents, colorants, heat resistance
stabilizers, UV stabilizers, foaming agents, rust inhibitors, flame
retardants, and lubricants; and examples of additives that may be
appropriately added depending on the application include synthetic
resins such as polyester, polyamide, polyimide, polyetherimide,
polycarbonate, polyphenylene ether, polysulfone, polyether sulfone,
polyether ether ketone, polyether ketone, polyarylene,
polyethylene, polypropylene, polytetrafluoroethylene,
polydifluoroethylene, polystyrene, ABS resins, epoxy resins,
silicone resins, phenol resins, urethane resins, and liquid crystal
polymers; elastomers such as polyolefin-based rubber, fluororubber,
and silicone rubber; and coupling agents such as silane coupling
agents. Such additives used in the present invention are not
essential components. However, the additives are preferably added
in an amount of more than 0 parts by mass, and generally in an
amount of 10 parts by mass or more and 500 parts by mass or less
with respect to 100 parts by mass of the polyarylene sulfide resin
because various performances can be improved depending on the
purpose of the additive added.
[0061] For a long fiber-reinforced polyarylene sulfide resin molded
article according to the present invention, a long fiber-reinforced
polyarylene sulfide resin composition used in the present invention
is dry-blended with a polyarylene sulfide resin.
[0062] The proportions of the long fiber-reinforced polyarylene
sulfide resin composition and the polyarylene sulfide resin (a2)
are not particularly limited as long as advantageous effects
provided by the present invention are not impaired; however, with
respect to the total 100 parts by mass of the long fiber-reinforced
polyarylene sulfide resin composition and the polyarylene sulfide
resin (a2), the proportion of the long fiber-reinforced polyarylene
sulfide resin composition is preferably 2 to 98 parts by mass, and
the proportion of the polyarylene sulfide resin (a2) is preferably
98 to 2 parts by mass; more preferably, the proportion of the long
fiber-reinforced polyarylene sulfide resin composition is 5 to 95
parts by mass, and the proportion of the polyarylene sulfide resin
(a2) is 95 to 5 parts by mass; and particularly preferably, the
proportion of the long fiber-reinforced polyarylene sulfide resin
composition is 10 to 90 parts by mass, and the proportion of the
polyarylene sulfide resin (a2) is 90 to 10 parts by mass.
[0063] When, as a component dry-blended with the long
fiber-reinforced polyarylene sulfide resin composition, the
thermoplastic elastomer (b2) is further added to the polyarylene
sulfide resin (a2), the proportions of the long fiber-reinforced
polyarylene sulfide resin composition, the polyarylene sulfide
resin (a2), and the thermoplastic elastomer (b2) are not
particularly limited as long as advantageous effects provided by
the present invention are not impaired; however, with respect to
the total 100 parts by mass of the long fiber-reinforced
polyarylene sulfide resin composition, the polyarylene sulfide
resin (a2), and the thermoplastic elastomer (b2), the proportion of
the long fiber-reinforced polyarylene sulfide resin composition is
preferably 2 to 98 parts by mass, and the total proportion of the
polyarylene sulfide resin (a2) and the thermoplastic elastomer (b2)
is preferably 98 to 2 parts by mass; more preferably, the
proportion of the long fiber-reinforced polyarylene sulfide resin
composition is 5 to 95 parts by mass, and the total proportion of
the polyarylene sulfide resin (a2) and the thermoplastic elastomer
(b2) is 95 to 5 parts by mass; and particularly preferably, the
proportion of the long fiber-reinforced polyarylene sulfide resin
composition is 10 to 90 parts by mass, and the total proportion of
the polyarylene sulfide resin (a2) and the thermoplastic elastomer
(b2) is 90 to 10 parts by mass.
[0064] In this case, the proportions of the polyarylene sulfide
resin (a2) and the thermoplastic elastomer (b2) are not
particularly limited as long as advantageous effects provided by
the present invention are not impaired; however, with respect to
the total 100 parts by mass of the polyarylene sulfide resin (a2)
and the thermoplastic elastomer (b2), the proportion of the
polyarylene sulfide resin (a2) is preferably 99.9 to 50 parts by
mass, and the proportion of the thermoplastic elastomer (b2) is
preferably 0.1 to 50 parts by mass; more preferably, the proportion
of the polyarylene sulfide resin (a2) is 99 to 70 parts by mass,
and the proportion of the thermoplastic elastomer (b2) is 1 to 30
parts by mass; and particularly preferably, the proportion of the
polyarylene sulfide resin (a2) is 95 to 80 parts by mass, and the
proportion of the thermoplastic elastomer (b2) is 5 to 20 parts by
mass.
[0065] In the dry blending, the shapes of the polyarylene sulfide
resin (a2) and the thermoplastic elastomer (b2) are not
particularly limited; and examples of the shapes include powder,
particles, granules, strands, rods, needles, plates, tubes, blocks,
and pellets. The shape of pellets is preferred because the resin
and the elastomer can be easily and uniformly mixed.
[0066] The dry blending may be performed by a known method: for
example, the long fiber-reinforced polyarylene sulfide resin
composition, the polyarylene sulfide resin, and the thermoplastic
elastomer (b2), which is added as necessary, may be put into a
ribbon blender, a Henschel mixer, a V blender, or the like, and
dry-blended, to prepare a dry-blended substance.
[0067] Such a dry-blended substance obtained in this manner and
used in the present invention is appropriately prepared in
accordance with the types and proportions of the polyarylene
sulfide resin, the fiber reinforcing material, and the
thermoplastic elastomer used as necessary. In particular, in the
case of performing blow hollow molding, the melt flow rate is
preferably set to 10 to 100 g/10 min, more preferably 20 to 80 g/10
min, still more preferably 30 to 60 g/10 min. Such a range is
preferably satisfied because variations in the thickness of the
molded article tend to be suppressed, to thereby provide a blow
molded article having excellent uniformity. In addition, a melt
flow rate of 10 g/10 min or higher is preferably satisfied because
gelation tends to be suppressed.
[0068] Incidentally, the melt flow rate is determined by putting
the dry-blended substance into a melt indexer at a cylinder
temperature of 316.degree. C. with an orifice diameter of 3 mm,
applying a load of 10 kg, and, after preheating for 5 minutes,
measuring the melt flow rate (g/10 min).
[0069] Regarding a long fiber-reinforced polyarylene sulfide resin
molded article according to the present invention, dry blending is
performed to maintain excellent heat resistance of the polyarylene
sulfide resin, and a fiber reinforcing material having a large
fiber length is contained to thereby provide a molded article
having more excellent mechanical properties such as impact
resistance. In particular, a blow-molded hollow article can be
provided that maintains the excellent heat resistance of the
polyarylene sulfide resin, that is also excellent in moldability in
terms of draw-down properties and thickness unevenness during blow
hollow molding, and that is also excellent in mechanical strengths
such as impact resistance.
[0070] The obtained dry-blended substance is subsequently melted,
turned into a melted and kneaded substance, and extruded. The
melted and kneaded substance may be temporarily processed into
pellets or the like, or may be directly molded by blow hollow
molding or the like.
[0071] When the obtained dry-blended substance is melted, it is
heated at a temperature not less than the melting point of the
polyarylene sulfide resin. When the polyarylene sulfide resin (a1)
and the polyarylene sulfide resin (a2) have different melting
points, the heating is performed at a temperature not less than the
higher melting point. When the dry-blended substance is melted and
turned into a melted and kneaded substance and then temporarily
processed into pellets or the like, the pellets or the like are
heated and melted again, as with the dry-blended substance, at a
temperature not less than the melting point of the polyarylene
sulfide resin, and then molded by blow hollow molding or the
like.
[0072] The molding method may be a known method as long as
advantageous effects provided by the present invention are not
impaired. For example, preferably, the dry-blended substance is
supplied to a melt extruder having a single screw, heated and
melted at a temperature not less than the melting point of the
polyarylene sulfide resin, preferably heated and melted at 290 to
320.degree. C., melt-extruded, and then molded.
[0073] More specifically, for example, the following method may be
employed: melt-extrusion is performed under conditions at a screw
rotation speed of 50 to 250 rpm and at a discharge rate of 5 to 25
kg/h; and then molding into the intended molded article is
performed. In the case of blow molding, for example, the following
method may be employed: after melt-extrusion, a parison is formed
with a die gap of 1 to 10 mm, and is subsequently molded into the
intended two- or three-dimensional molded hollow article.
[0074] Examples of the screw form include full-flight-type single
screws, and single screws having a mixing mechanism of, for
example, a Dulmage type, a Maddock type, or a pin-equipped type.
Since fragmentation of the fiber reinforcing material by shearing
during melting of the resin can be suppressed, single screws that
have a compression ratio of 2 or less are preferably used; more
preferably, single screws that have a compression ratio of 2 or
less and 1 or more are used; particularly preferably, single screws
that are full-flight-type single screws and have a compression
ratio of 2 or less are used.
[0075] The effective length (L/D) is not particularly limited as
long as it is a value used for molding a normal polyarylene sulfide
resin. The effective length (L/D) is, for example, 1 to 100,
preferably 5 to 50.
[0076] Various molding methods can be performed such as injection
molding; compression molding; extrusion molding for composites,
sheets, pipes, or the like; pultrusion molding; blow molding; or
transfer molding. In particular, the blow molding method is
preferred because it provides excellent moldability in terms of
draw-down resistance or thickness unevenness. Representative
examples of the blow molding method include a direct blow method,
an accumulator blow method, and a multi-dimensional blow method.
Alternatively, it is clearly possible to employ a multilayer blow
molding method, an exchange blow molding method, or the like, which
are used in the case of combination with another material.
[0077] A long fiber-reinforced polyarylene sulfide resin molded
article according to the present invention obtained in this manner
contains a polyarylene sulfide resin and a fiber reinforcing
material that has a fiber length of more than 5 mm, preferably more
than 5 mm and 30 mm or less, more preferably 6 mm or more and 20 mm
or less, still more preferably 10 mm or more and 15 mm or less. In
particular, in the case of blow-molded hollow articles, as in
dry-blended substances, the melt flow rate is preferably set to 10
to 100 g/10 min, more preferably 20 to 80 g/10 min, still more
preferably 30 to 60 g/10 min.
[0078] In a long fiber-reinforced polyarylene sulfide resin molded
article according to the present invention, the proportions of the
polyarylene sulfide resin, the fiber reinforcing material, and the
thermoplastic elastomer, which is added as necessary, are the same
as the proportions of the total amounts of the components added as
raw materials in the above-described production method:
specifically, the proportion of the total amount of the polyarylene
sulfide resin (a1) and the polyarylene sulfide resin (a2), the
proportion of the fiber reinforcing material, and the proportion of
the total amount of the thermoplastic elastomer (b1) and the
thermoplastic elastomer (b2), which are added as necessary.
However, with respect to the total 100 parts by mass of the
polyarylene sulfide resin and the fiber reinforcing material, the
proportion of the polyarylene sulfide resin is preferably 99 to 25
parts by mass, and the proportion of the fiber reinforcing material
is preferably 1 to 75 parts by mass; more preferably, the
proportion of the polyarylene sulfide resin is 95 to 35 parts by
mass, and the proportion of the fiber reinforcing material is 5 to
65 parts by mass. When the thermoplastic elastomer is added as
necessary, with respect to the total 100 parts by mass of the
polyarylene sulfide resin, the fiber reinforcing material, and the
thermoplastic elastomer, the proportion of the polyarylene sulfide
resin is preferably 98 to 24 parts by mass, the proportion of the
fiber reinforcing material is preferably 1 to 74 parts by mass, and
the proportion of the thermoplastic elastomer is preferably 0.1 to
30; more preferably, the proportion of the polyarylene sulfide
resin is 94 to 34 parts by mass, the proportion of the fiber
reinforcing material is 4 to 64 parts by mass, and the proportion
of the thermoplastic elastomer is 1 to 20.
[0079] A long fiber-reinforced polyarylene sulfide resin molded
article according to the present invention has excellent
moldability, and is also excellent in various performances such as
heat resistance, dimensional stability, and chemical resistance,
which are inherent in polyarylene sulfide resins, and mechanical
strengths such as impact resistance and thermal shock resistance.
Thus, the molded article can be widely used not only for
injection-molded articles, compression-molded articles, or
metal-inserted molded articles for, for example, electrical or
electronic components such as connectors, printed boards, and
sealing-molded articles, automobile parts such as reflector lamps
and various electrical components, interior materials for various
buildings, aircraft, automobiles, and the like, OA equipment parts,
and precision parts such as camera parts and watch components, but
also for, as a molded hollow article such as a bottle, a tank, or a
duct, containers for medicinal solutions, air-conditioning ducts,
ducts and pipes for high-temperature gases discharged from internal
combustion engines such as those for automobiles or fuel cells, and
the like.
EXAMPLES
[0080] Hereinafter, the present invention will be specifically
described with reference to examples; however, the present
invention is not limited only to these examples.
Production Examples 1 to 3
Production of Long Fiber-Reinforced Polyarylene Sulfide Resin
Compositions
[0081] While a polyarylene sulfide resin described in Table 1 was
put into a twin-screw extruder, and melted and kneaded at a resin
composition discharge rate of 25 kg/hr, a screw rotation speed of
250 rpm, and a cylinder setting temperature of 310.degree. C., a
roving (fiber diameter: 10 .mu.m) of glass fibers described in
Table 1 was continuously supplied to an impregnation die installed
at the tip of the extruder so as to satisfy a proportion described
in Table 1, and was extruded to prepare a strand-like material in
which the glass fibers were coated with the melted polyarylene
sulfide resin. Then, the strand-like material was cooled with air
to 23.degree. C. to obtain a strand, and the strand was cut to a
length of 10 mm using a strand cutter to thereby obtain
fiber-reinforced polyarylene sulfide resin composition pellets
(CP).
TABLE-US-00001 TABLE 1 Production Production Production Example 1
Example 2 Example 3 CP1 CP2 CP3 PPS (1) PPS (2) 80.0 60.0 40.0 PPS
(3) Fiber Reinforcing 20.0 40.0 60.0 Material (1) Fiber Reinforcing
Material (2) Polyolefin (1) Polyolefin (2) Polyolefin (3)
Production Examples 4 to 6
Production of Polyolefin Resin-Containing Polyarylene Sulfide Resin
Compositions
[0082] A polyarylene sulfide resin and a polyolefin described in
Table 2 were put into a twin-screw extruder, and melted and kneaded
at a resin composition discharge rate of 25 kg/hr, a screw rotation
speed of 250 rpm, and a cylinder setting temperature of 310.degree.
C., and subsequently extruded through a T die installed at the tip
of the extruder to thereby produce a strand-like material. After
that, the strand-like material was cooled with air to 23.degree. C.
to obtain a strand, and the strand was cut to a length of 10 mm
using a strand cutter to thereby obtain polyarylene sulfide resin
composition pellets (CP).
TABLE-US-00002 TABLE 2 Production Production Production Production
Production Example 4 Example 5 Example 6 Example 7 Example 8 CP4
CP5 CP6 CP7 CP8 PPS (1) PPS (2) 86.0 86.0 86.0 99.0 70.0 PPS (3)
Fiber Reinforcing Material (1) Fiber Reinforcing Material (2)
Polyolefin (1) 14.0 1.0 30.0 Polyolefin (2) 14.0 Polyolefin (3)
14.0
Production Examples 9 to 11
Production of Polyolefin Resin-Containing Long Fiber-Reinforced
Polyarylene Sulfide Resin Compositions
[0083] As described in Table 3, a polyarylene sulfide resin and a
polyolefin resin were mixed with a Henschel mixer at proportions
described in Table 3. Subsequently, the mixture was put into a
twin-screw extruder. While the mixture was melted and kneaded at a
resin composition discharge rate of 25 kg/hr, a screw rotation
speed of 250 rpm, and a cylinder setting temperature of 310.degree.
C., a roving (fiber diameter: 10 .mu.m) of glass fibers described
in Table 1 was continuously supplied to an impregnation die
installed at the tip of the extruder so as to satisfy a proportion
described in Table 1 and extrusion was performed to prepare a
strand-like material in which the glass fibers were coated with the
melted polyarylene sulfide resin and polyolefin resin. After that,
the strand-like material was cooled with air to 23.degree. C. to
obtain a strand, and the strand was cut to a length of 10 mm using
a strand cutter to thereby obtain fiber-reinforced polyarylene
sulfide resin composition pellets (CP).
TABLE-US-00003 TABLE 3 Production Production Production Example 9
Example 10 Example 11 CP9 CP10 CP11 PPS (1) PPS (2) 66.0 46.0 26.0
PPS (3) Fiber Reinforcing 20.0 40.0 60.0 Material (1) Fiber
Reinforcing Material (2) Polyolefin (1) 14.0 14.0 14.0 Polyolefin
(2) Polyolefin (3)
Production Examples 12 to 14
Production of Short Fiber Reinforcing Material-Containing
Polyarylene Sulfide Resin Compositions
[0084] A polyarylene sulfide resin described in Table 4 was put
into a twin-screw extruder, and glass fibers were supplied through
a side feeder 1 as described in Table 4. These materials were
melted and kneaded at a resin composition discharge rate of 25
kg/hr, a screw rotation speed of 250 rpm, and a cylinder setting
temperature of 310.degree. C., and subsequently extruded through a
T die installed at the tip of the extruder to prepare a strand-like
material. After that, the strand-like material was cooled with air
to 23.degree. C. to obtain a strand, and the strand was cut to a
length of 10 mm using a strand cutter to thereby obtain polyarylene
sulfide resin composition pellets (CP).
TABLE-US-00004 TABLE 4 Production Production Production Example 12
Example 13 Example 14 CP12 CP13 CP14 PPS (1) PPS (2) 80.0 60.0 40.0
PPS (3) Fiber Reinforcing Material (1) Fiber Reinforcing 20.0 40.0
60.0 Material (2) Polyolefin (1) Polyolefin (2) Polyolefin (3)
Production Examples 15 to 17
Production of Polyolefin Resin- and Short Fiber Reinforcing
Material-Containing Polyarylene Sulfide Resin Compositions
[0085] A polyarylene sulfide resin and a polyolefin resin described
in Table 5 were put into a twin-screw extruder, and glass fibers
were supplied through a side feeder as described in Table 5. These
materials were melted and kneaded at a resin composition discharge
rate of 25 kg/hr, a screw rotation speed of 250 rpm, and a cylinder
setting temperature of 310.degree. C., and subsequently extruded
through a T die installed at the tip of the extruder to prepare a
strand-like material. After that, the strand-like material was
cooled with air to 23.degree. C. to obtain a strand, and the strand
was cut to a length of 10 mm using a strand cutter to thereby
obtain polyarylene sulfide resin composition pellets (CP).
TABLE-US-00005 TABLE 5 Production Production Production Example 15
Example 16 Example 17 CP15 CP16 CP17 PPS (1) PPS (2) 66.0 46.0 26.0
PPS (3) Fiber Reinforcing Material (1) Fiber Reinforcing 20.0 40.0
60.0 Material (2) Polyolefin (1) 14.0 14.0 14.0 Polyolefin (2)
Polyolefin (3)
Examples 1 to 7
Preparation of Dry-Blended Substances
[0086] As described in Table 6, the long fiber-reinforced
polyarylene sulfide resin composition pellets (CPs 1 to 3) and
polyarylene sulfide resins were put into a "MAZEMAZE MAN HBT-500)
manufactured by MISUGI LTD., and dry-blended to obtain dry-blended
substances (DBs 1 to 7).
[0087] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 6).
TABLE-US-00006 TABLE 6 Examples 1 2 3 4 5 6 7 DB1 DB2 DB3 DB4 DB5
DB6 DB7 PPS (1) PPS (2) 75.0 87.5 91.5 62.5 75.0 17.0 PPS (3) 75.0
CP1 25.0 25.0 CP2 12.5 37.5 CP3 8.5 25.0 83.0 Evaluations for
Dry-Blended Substances Fiber Reinforcing Material 5.0 5.0 5.0 5.0
15.0 15.0 50.0 Content (wt %) Number-Average Fiber 10 10 10 10 10
10 10 Length of Fiber Reinforcing Material (mm) Aspect Ratio of
Fiber 1000 1000 1000 1000 1000 1000 1000 Reinforcing Material MFR
(g/10 min) 90 43 90 90 76 76 20 Draw-Down .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Resistance/Extrusion Stability
(Production of Blow-Molded Articles)
[0088] Subsequently, the obtained dry-blended substances (DBs 1 to
7) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1), and extruded at a resin composition
discharge rate of 25 kg/hr, a screw rotation speed of 250 rpm, and
a cylinder setting temperature of 290.degree. C. to form a parison
having an outer diameter of 30 mm and a thickness of 4 mm. After
that, air was blown into the parison within the mold, to thereby
form a cylindrical container having a height of 250 mm, an outer
diameter of 50 mm, and a thickness of approximately 2 to 3 mm.
[0089] The obtained blow-molded hollow articles were subjected to
measurements (Table 7).
TABLE-US-00007 TABLE 7 Examples 1 2 3 4 5 6 7 DB1 DB2 DB3 DB4 DB5
DB6 DB7 Evaluations for Blow-Molded Hollow Articles Number-Average
10 10 10 10 10 10 10 Fiber Length of Fiber Reinforcing Material
(mm) Inner-Surface .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .largecircle.
Smoothness Thickness .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .largecircle.
Uniformity Heat Resistance .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. Impact Resistance 18 20 18 18 25 25 70
(kJ/m.sup.2)
Examples 8 to 14
(Preparation of Dry-Blended Substances)
[0090] As described in Table 8, the polyolefin resin-containing
long fiber-reinforced polyarylene sulfide resin composition pellets
(CPs 9 to 11) and polyarylene sulfide resins were put into a
"MAZEMAZE MAN HBT-500) manufactured by MISUGI LTD. and dry-blended
to obtain dry-blended substances (DBs 9 to 16).
[0091] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 8).
TABLE-US-00008 TABLE 8 Examples 8 9 10 11 12 13 14 DB8 DB9 DB10
DB11 DB12 DB13 DB14 PPS (1) PPS (2) 75.0 87.5 91.5 62.5 75.0 17.0
PPS (3) 75.0 CP9 25.0 25.0 CP10 12.5 37.5 CP11 8.5 25.0 83.0
Evaluations for Dry-Blended Substances Fiber Reinforcing Material
5.0 5.0 5.0 5.0 15.0 15.0 50.0 Content (wt %) Number-Average Fiber
10 10 10 10 10 10 10 Length of Fiber Reinforcing Material (mm)
Aspect Ratio of Fiber 1000 1000 1000 1000 1000 1000 1000
Reinforcing Material MFR (g/10 min) 80 38 84 88 56 60 14 Draw-Down
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Resistance/Extrusion
Stability
(Production of Blow-Molded Articles)
[0092] Subsequently, the obtained dry-blended substances (DBs 9 to
16) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1), and extruded at a resin composition
discharge rate of 25 kg/hr, a screw rotation speed of 250 rpm, and
a cylinder setting temperature of 290.degree. C. to form a parison
having an outer diameter of 30 mm and a thickness of 4 mm. After
that, air was blown into the parison within the mold, to thereby
form a cylindrical container having a height of 250 mm, an outer
diameter of 50 mm, and a thickness of approximately 2 to 3 mm.
[0093] The obtained blow-molded hollow articles were subjected to
measurements (Table 9).
TABLE-US-00009 TABLE 9 Examples 8 9 10 11 12 13 14 DB8 DB9 DB10
DB11 DB12 DB13 DB14 Evaluations for Blow-Molded Hollow Articles
Number-Average 10 10 10 10 10 10 10 Fiber Length of Fiber
Reinforcing Material (mm) Inner-Surface .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .largecircle. Smoothness Thickness .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .largecircle. Uniformity Heat Resistance
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Impact Resistance 30
32 26 25 46 43 104 (kJ/m.sup.2)
Examples 15 to 22
(Preparation of Dry-Blended Substances)
[0094] As described in Table 10, the long fiber-reinforced
polyarylene sulfide resin composition pellets (CPs 1 to 3) and
polyolefin resin-containing polyarylene sulfide resins (CPs 4 to 8)
were put into a "MAZEMAZE MAN HBT-500) manufactured by MISUGI LTD.
and dry-blended to obtain dry-blended substances (DBs 15 to
22).
[0095] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 10).
TABLE-US-00010 TABLE 10 Examples 15 16 17 18 19 21 22 DB15 DB16
DB17 DB18 DB19 DB21 DB22 CP1 25.0 25.0 25.0 25.0 CP2 37.5 CP3 25.0
83.0 CP4 75.0 62.5 75.0 17.0 CP5 75.0 CP6 75.0 CP7 CP8 75.0
Evaluations for Dry-Blended Substances Fiber Reinforcing Material
5.0 5.0 5.0 5.0 15.0 15.0 50.0 Content (wt %) Number-Average Fiber
Length 10 10 10 10 10 10 10 of Fiber Reinforcing Material (mm)
Aspect Ratio of Fiber 1000 1000 1000 1000 1000 1000 1000
Reinforcing Material MFR (g/10 min) 73 78 80 76 50 47 18 Draw-Down
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Resistance/Extrusion
Stability
(Production of Blow-Molded Articles)
[0096] Subsequently, the obtained dry-blended substances (DBs 15 to
22) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1, and an effective length L/D ratio of 30),
and extruded at a resin composition discharge rate of 25 kg/hr, a
screw rotation speed of 250 rpm, and a cylinder setting temperature
of 290.degree. C. to form a parison having an outer diameter of 30
mm and a thickness of 4 mm. After that, air was blown into the
parison within the mold, to thereby form a cylindrical container
having a height of 250 mm, an outer diameter of 50 mm, and a
thickness of approximately 2 to 3 mm.
[0097] The obtained blow-molded hollow articles were subjected to
measurements (Table 11).
TABLE-US-00011 TABLE 11 Examples 15 16 17 18 19 21 22 DB15 DB16
DB17 DB18 DB19 DB21 DB22 Evaluations for Blow-Molded Hollow
Articles Number-Average 10 10 10 10 10 10 10 Fiber Length of Fiber
Reinforcing Material (mm) Inner-Surface .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .largecircle. Smoothness Thickness .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .largecircle. Uniformity Heat Resistance
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Impact Resistance 50
48 45 35 49 52 85 (kJ/m.sup.2)
Examples 23 to 30
(Preparation of Dry-Blended Substances)
[0098] As described in Table 12, the polyolefin resin-containing
long fiber-reinforced polyarylene sulfide resin composition pellets
(CPs 9 to 11) and the polyolefin resin-containing polyarylene
sulfide resin compositions (CPs 4 to 8) were put into a "MAZEMAZE
MAN HBT-500) manufactured by MISUGI LTD. and dry-blended to obtain
dry-blended substances (DBs 23 to 30).
[0099] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 12).
TABLE-US-00012 TABLE 12 Examples 23 24 25 26 27 28 29 30 DB23 DB24
DB25 DB26 DB27 DB28 DB29 DB30 CP9 25.0 25.0 25.0 25.0 25.0 CP10
37.5 CP11 25.0 83.0 CP4 75.0 62.5 75.0 17.0 CP5 75.0 CP6 75.0 CP7
75.0 CP8 75.0 Evaluations for Dry-Blended Substances Fiber
Reinforcing Material 5.0 5.0 5.0 5.0 5.0 15.0 15.0 50.0 Content (wt
%) Number-Average Fiber 10 10 10 10 10 10 10 10 Length of Fiber
Reinforcing Material (mm) Aspect Ratio of Fiber 1000 1000 1000 1000
1000 1000 1000 1000 Reinforcing Material MFR (g/10 min) 72 75 77 79
75 50 50 12 Draw-Down .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Resistance/Extrusion Stability
(Production of Blow-Molded Articles)
[0100] Subsequently, the obtained dry-blended substances (DBs 23 to
30) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1, and an effective length L/D ratio of 30),
and extruded at a resin composition discharge rate of 25 kg/hr, a
screw rotation speed of 250 rpm, and a cylinder setting temperature
of 290.degree. C. to form a parison having an outer diameter of 30
mm and a thickness of 4 mm. After that, air was blown into the
parison within the mold, to thereby form a cylindrical container
having a height of 250 mm, an outer diameter of 50 mm, and a
thickness of approximately 2 to 3 mm.
[0101] The obtained blow-molded hollow articles were subjected to
measurements (Table 13).
TABLE-US-00013 TABLE 13 Examples 23 24 25 26 27 28 29 30 DB23 DB24
DB25 DB26 DB27 DB28 DB29 DB30 Evaluations for Blow-Molded Hollow
Articles Number-Average Fiber 10 10 10 10 10 10 10 10 Length of
Fiber Reinforcing Material (mm) Inner-Surface Smoothness
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .largecircle.
Thickness Uniformity .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.largecircle. Heat Resistance .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. Impact Resistance (kJ/m.sup.2) 55 53
52 32 44 67 67 120
Examples 31 to 35
(Preparation of Dry-Blended Substances)
[0102] As described in Table 14, the long fiber-reinforced
polyarylene sulfide resin composition pellets (CPs 1 to 3) and the
short fiber reinforcing material-containing polyarylene sulfide
resin compositions (CPs 12 to 14) were put into a "MAZEMAZE MAN
HBT-500) manufactured by MISUGI LTD. and dry-blended to obtain
dry-blended substances (DBs 31 to 35).
[0103] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 14).
TABLE-US-00014 TABLE 14 Examples 31 32 33 34 35 DB31 DB32 DB33 DB34
DB35 CP1 50.0 50.0 50.0 CP2 50.0 CP3 50.0 CP12 50.0 50.0 50.0 CP13
50.0 CP14 50.0 Evaluations for Dry-Blended Substances Fiber
Reinforcing Material 20.0 30.0 40.0 30.0 40.0 Content (wt %)
Number-Average Fiber Length 5.2 3.5 2.8 6.8 7.8 of Fiber
Reinforcing Material (mm) Average Aspect Ratio of Fiber 520 350 280
680 780 Reinforcing Material MFR (g/10 min) 78 74 72 65 48
Draw-Down .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Resistance/Extrusion Stability
(Production of Blow-Molded Articles)
[0104] Subsequently, the obtained dry-blended substances (DBs 31 to
35) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1, and an effective length L/D ratio of 30),
and extruded at a resin composition discharge rate of 25 kg/hr, a
screw rotation speed of 250 rpm, and a cylinder setting temperature
of 290.degree. C. to form a parison having an outer diameter of 30
mm and a thickness of 4 mm. After that, air was blown into the
parison within the mold, to thereby form a cylindrical container
having a height of 250 mm, an outer diameter of 50 mm, and a
thickness of approximately 2 to 3 mm.
[0105] The obtained blow-molded hollow articles were subjected to
measurements (Table 15).
TABLE-US-00015 TABLE 15 Examples 31 32 33 34 35 DB31 DB32 DB33 DB34
DB35 Evaluations for Blow-Molded Hollow Articles Number-Average
Fiber 5.2 3.5 2.8 6.8 7.8 Length of Fiber Reinforcing Material (mm)
Inner-Surface Smoothness .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Thickness Uniformity
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. Heat Resistance .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Impact Resistance
(kJ/m.sup.2) 22 24 25 32 52
Examples 36 to 40
(Preparation of Dry-Blended Substances)
[0106] As described in Table 16, the polyolefin resin-containing
long fiber-reinforced polyarylene sulfide resin composition pellets
(CPs 9 to 11) and the short fiber reinforcing material-containing
polyarylene sulfide resin compositions (CPs 12 to 14) were put into
a "MAZEMAZE MAN HBT-500) manufactured by MISUGI LTD. and
dry-blended to obtain dry-blended substances (DBs 36 to 40).
[0107] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 16).
TABLE-US-00016 TABLE 16 Examples 36 37 38 39 40 DB36 DB37 DB38 DB39
DB40 CP9 50.0 50.0 50.0 CP10 50.0 CP11 50.0 CP12 50.0 50.0 50.0
CP13 50.0 CP14 50.0 Evaluations for Dry-Blended Substances Fiber
Reinforcing Material 20.0 30.0 40.0 30.0 40.0 Content (wt %)
Number-Average Fiber 5.2 3.5 2.8 6.8 7.8 Length of Fiber
Reinforcing Material (mm) Average Aspect Ratio of Fiber 520 350 280
680 780 Reinforcing Material MFR (g/10 min) 64 63 62 52 36
Draw-Down .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Resistance/Extrusion Stability
(Production of Blow-Molded Articles)
[0108] Subsequently, the obtained dry-blended substances (DBs 36 to
40) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1, and an effective length L/D ratio of 30),
and extruded at a resin composition discharge rate of 25 kg/hr, a
screw rotation speed of 250 rpm, and a cylinder setting temperature
of 290.degree. C. to form a parison having an outer diameter of 30
mm and a thickness of 4 mm. After that, air was blown into the
parison within the mold, to thereby form a cylindrical container
having a height of 250 mm, an outer diameter of 50 mm, and a
thickness of approximately 2 to 3 mm.
[0109] The obtained blow-molded hollow articles were subjected to
measurements (Table 17).
TABLE-US-00017 TABLE 17 Examples 36 37 38 39 40 DB36 DB37 DB38 DB39
DB40 Evaluations for Blow-Molded Hollow Articles Number-Average
Fiber 5.2 3.5 2.8 6.8 7.8 Length of Fiber Reinforcing Material (mm)
Inner-Surface Smoothness .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Thickness Uniformity
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. Heat Resistance .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Impact Resistance
(kJ/m.sup.2) 35 36 37 50 72
Examples 41 to 45
(Preparation of Dry-Blended Substances)
[0110] As described in Table 18, the long fiber-reinforced
polyarylene sulfide resin composition pellets (CPs 1 to 3) and the
polyolefin- and short fiber reinforcing material-containing
polyarylene sulfide resin compositions (CPs 15 to 17) were put into
a "MAZEMAZE MAN HBT-500" manufactured by MISUGI LTD. and
dry-blended to obtain dry-blended substances (DBs 41 to 45).
[0111] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 18).
TABLE-US-00018 TABLE 18 Examples 41 42 43 44 45 DB41 DB42 DB43 DB44
DB45 CP1 50.0 50.0 50.0 CP2 50.0 CP3 50.0 CP15 50.0 50.0 50.0 CP16
50.0 CP17 50.0 Evaluations for Dry-Blended Substances Fiber
Reinforcing Material 20.0 30.0 40.0 30.0 40.0 Content (wt %)
Number-Average Fiber 5.2 3.5 2.8 6.8 7.8 Length of Fiber
Reinforcing Material (mm) Average Aspect Ratio of Fiber 520 350 280
680 780 Reinforcing Material MFR (g/10 min) 64 63 62 52 36
Draw-Down .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Resistance/Extrusion Stability
(Production of Blow-Molded Articles)
[0112] Subsequently, the obtained dry-blended substances (DBs 41 to
45) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1, and an effective length L/D ratio of 30),
and extruded at a resin composition discharge rate of 25 kg/hr, a
screw rotation speed of 250 rpm, and a cylinder setting temperature
of 290.degree. C. to form a parison having an outer diameter of 30
mm and a thickness of 4 mm. After that, air was blown into the
parison within the mold, to thereby form a cylindrical container
having a height of 250 mm, an outer diameter of 50 mm, and a
thickness of approximately 2 to 3 mm.
[0113] The obtained blow-molded hollow articles were subjected to
measurements (Table 19).
TABLE-US-00019 TABLE 19 Examples 41 42 43 44 45 DB41 DB42 DB43 DB44
DB45 Evaluations for Blow-Molded Hollow Articles Number-Average
Fiber 5.2 3.5 6.8 7.8 10.0 Length of Fiber Reinforcing Material
(mm) Inner-Surface Smoothness .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Thickness Uniformity
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. Heat Resistance .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Impact Resistance
(kJ/m.sup.2) 35 36 37 50 72
Comparative Examples 1 to 6
(Preparation of Dry-Blended Substances)
[0114] As described in Table 20, the polyarylene sulfide resins (1
to 3) and the polyolefin- and short fiber reinforcing
material-containing polyarylene sulfide resin compositions (CPs 15
to 17) were put into a "MAZEMAZE MAN HBT-500" manufactured by
MISUGI LTD. and dry-blended to obtain dry-blended substances (DBs
46 to 51).
[0115] A portion of such an obtained dry-blended substance was
sampled and subjected to measurements (Table 20).
TABLE-US-00020 TABLE 20 Comparative Examples 1 2 3 4 5 6 DB46 DB47
DB48 DB49 DB50 DB51 PPS (1) 75.0 50.0 75.0 50.0 CP12 25.0 50.0 CP13
50.0 50.0 CP15 25.0 50.0 CP17 50.0 50.0 Evaluations for Dry-Blended
Substances Fiber Reinforcing Material 5 30 5 30 20 40 Content (wt
%) Number-Average Fiber 0.3 0.3 0.3 0.3 0.3 0.3 Length of Fiber
Reinforcing Material (mm) Aspect Ratio of Fiber 30 30 30 30 30 30
Reinforcing Material MFR (g/10 min) 900 580 750 300 550 220
Draw-Down X X X X X X Resistance/Extrusion Stability
(Production of Blow-Molded Articles)
[0116] Subsequently, the obtained dry-blended substances (DBs 46 to
51) were each supplied to a blow molding machine equipped with a
.phi.45 mm-extruder (a full-flight-type single screw having a
compression ratio of 1, and an effective length L/D ratio of 30),
and extruded at a resin composition discharge rate of 25 kg/hr, a
screw rotation speed of 250 rpm, and a cylinder setting temperature
of 290.degree. C. to form a parison having an outer diameter of 30
mm and a thickness of 4 mm. After that, air was blown into the
parison within the mold, to thereby form a cylindrical container
having a height of 250 mm, an outer diameter of 50 mm, and a
thickness of approximately 2 to 3 mm.
[0117] The obtained blow-molded hollow articles were subjected to
measurements (Table 21).
TABLE-US-00021 TABLE 21 Comparative Examples 1 2 3 4 5 6 DB46 DB47
DB48 DB49 DB50 DB51 Evaluations for Blow-Molded Hollow Articles
Number-Average Fiber 0.3 0.3 0.3 0.3 0.3 0.3 Length of Fiber
Reinforcing Material (mm) Inner-Surface Smoothness .largecircle.
.largecircle. .largecircle. .circle-w/dot. .circle-w/dot.
.circle-w/dot. Thickness Uniformity .largecircle. .largecircle.
.largecircle. .circle-w/dot. .circle-w/dot. .circle-w/dot. Heat
Resistance .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Impact Resistance
(kJ/m.sup.2) 25 35 33 39 38 43
[0118] Several tests were performed as follows.
[0119] [Melt Viscosity (MFR)/Draw-Down Resistance/Extrusion
Stability]
[0120] The dry-blended substances obtained in Examples 1 to 45 and
Comparative Examples 1 to 6 were put into a melt indexer (cylinder
temperature: 316.degree. C., orifice diameter: 3 mm), and, after
preheating for 5 minutes, a melt flow rate (MFR) was measured under
application of a load of 10 kg.
[0121] The obtained melt viscosity was used as an index of
draw-down resistance and extrusion stability during blow molding;
substances having a melt viscosity of 100 to 10 g/10 min were
evaluated as ".largecircle." (good draw-down resistance and good
extrusion stability), substances having a melt viscosity of less
than 10 g/10 min were evaluated as ".DELTA." (poor extrusion
stability), and substances having a melt viscosity of more than 100
g/10 min were evaluated as "x" (poor draw-down resistance).
[0122] [Inner-Surface Smoothness]
[0123] An inner-surface maximum height Ry for 5 arbitrary points in
each of an upper portion (30 mm from the upper end) and a lower
portion (30 mm from the lower end) of the body of each of the blow
molded articles obtained in Examples 1 to 45 and Comparative
Examples 1 to 6 was evaluated on the basis of the following
criteria:
[0124] articles in which the maximum heights Ry were 0.2 mm or less
were evaluated as ".circle-w/dot.",
[0125] articles in which the maximum heights Ry were more than 0.2
mm and 0.5 mm or less were evaluated as ".largecircle.",
[0126] articles in which the maximum heights Ry were more than 0.5
mm and 1.0 mm or less were evaluated as ".DELTA.", and
[0127] articles in which the maximum heights Ry were more than 1.0
mm were evaluated as "x".
[0128] [Uniformity]
[0129] Thicknesses at 5 arbitrary points in each of an upper
portion (30 mm from the upper end) and a lower portion (30 mm from
the lower end) of the body of each of the blow molded articles
obtained in Examples 1 to 45 and Comparative Examples 1 to 6 were
measured, and the uniformity thereof was evaluated on the basis of
the following criteria:
[0130] articles in which the difference between the average
thickness of the upper portion and the average thickness of the
lower portion was within 0.2 mm were evaluated as
".circle-w/dot.",
[0131] articles in which the above difference in thickness was more
than 0.2 mm and 0.5 mm or less were evaluated as
".largecircle.",
[0132] articles in which the above difference in thickness was more
than 0.5 mm and 1.0 mm or less were evaluated as ".DELTA.", and
[0133] articles in which the above difference in thickness was more
than 1.0 mm were evaluated as "x".
[0134] [Heat Resistance]
[0135] The dry-blended substances obtained in Examples 1 to 45 and
Comparative Examples 1 to 6 were supplied to an injection molding
machine equipped with a .phi.45 mm-extruder (a full-flight-type
single screw having a compression ratio of 1, and an effective
length L/D ratio of 20), and injection-molded at a cylinder
temperature of 300.degree. C. and a mold temperature of 140.degree.
C. to form a dumbbell-shaped test piece for a tensile test. This
test piece was heated for 3,000 hours in an oven at 260.degree. C.,
taken out, and then measured for the tensile strength; and a
decrease from the tensile strength of the test piece which was not
heated was represented as a retention ratio (%). Test pieces having
a retention ratio of 80% or higher were evaluated as
".circle-w/dot.", test pieces having a retention ratio of 60% or
higher and less than 80% were evaluated as ".largecircle.", test
pieces having a retention ratio of 40% or higher and less than 60%
were evaluated as ".DELTA.", and test pieces having a retention
ratio of less than 40% were evaluated as "x".
[0136] [Impact Resistance]
[0137] A central portion of the dumbbell-shaped test piece for a
tensile test prepared in the heat resistance test was cut into a
rod shape having a length of 80 mm, a width of 10 mm, and a
thickness of 4 mm to serve as an impact resistance test piece. A
Charpy impact test was performed in accordance with ISO 179 to
measure the impact strength (kJ/mm.sup.2).
[Measurements of Fibers of Fiber Reinforcing Materials in Pellets
or Molded Articles]
[0138] The dry-blended substances or blow-molded hollow articles
obtained in Examples 1 to 45 and Comparative Examples 1 to 6 were
exposed for 2 h at 550.degree. C. in a muffle furnace; 500 glass
fibers contained in the ash were randomly picked, and measured for
fiber length and fiber diameter using a digital microscope; and a
number-average fiber length and a number-average fiber diameter
were calculated. From the values of the number-average fiber length
and the number-average fiber diameter obtained, a number-average
fiber length/number-average fiber diameter was calculated as an
aspect ratio.
[0139] Incidentally, the components described in Tables are as
follows and the values for the components are based on parts by
mass.
[0140] The raw materials in Tables are as follows.
[0141] PPS (1); polyphenylene sulfide resin "DIC.PPS" manufactured
by DIC Corporation (V6 melt viscosity: 30 Pas, non-NT index:
1.2)
[0142] PPS (2); polyphenylene sulfide resin "DIC.PPS" manufactured
by DIC Corporation (V6 melt viscosity: 50 Pas, non-NT index:
1.2)
[0143] PPS (3); polyphenylene sulfide resin "DIC.PPS" manufactured
by DIC Corporation (V6 melt viscosity: 150 Pas, non-NT index: 1.2)
[0144] The V6 melt viscosity of such a PPS resin is a value
measured using a flow tester CFT-500C manufactured by Shimadzu
Corporation after holding for 6 minutes at 300.degree. C. with a
load of 1.96.times.10.sup.6 Pa and L/D=10/1.
[0145] Fiber Reinforcing Material (1); Glass fiber roving (E-glass,
fiber diameter: 10 .mu.m, epoxy-based sizing agent)
[0146] Fiber Reinforcing Material (2); Glass fiber chopped strand
(E-glass, fiber diameter: 10 .mu.m, fiber length: 3 mm, epoxy-based
sizing agent)
[0147] Polyolefin (1): Ethylene-glycidyl methacrylate-methyl
acrylate copolymer "Bondfast-7L" manufactured by Sumitomo Chemical
Company, Limited
[0148] Polyolefin (2): Ethylene-maleic anhydride-ethyl acrylate
copolymer "BONDINE AX8390" manufactured by Arkema
[0149] Polyolefin (3): Ethylene-1-octene copolymer "ENGAGE 8842"
manufactured by The Dow Chemical Company
* * * * *